Adsorption of copolymers aggregates: From kinetics to adsorbed layer structure

Zdyrko, Bogdan; Ofir, Pazit Bar-Yosef; Alb, Alina M.; Reed, Wayne F.; Santore, Maria M.

doi:10.1016/j.jcis.2008.03.047

Cited by 9 publications

(15 citation statements)

References 51 publications

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“…It is well-known that PEG readily adsorbs to a variety of materials with high affinity and with no significant energy barriers [9, 64, 65]. Therefore, the adsorption of PEG is determined by the mass transfer rate from the bulk solution, making it reasonable to assume β = 1 [1].…”

Section: Resultsmentioning

confidence: 99%

Determination of a setup correction function to obtain adsorption kinetic data at stagnation point flow conditions

Mora

Nejadnik

Baylon-Cardiel

et al. 2010

Journal of Colloid and Interface Science

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This paper is the first report on the characterization of the hydrodynamic conditions in a flow cell designed to study adsorption processes by spectroscopic ellipsometry. The resulting cell enables combining the advantages of in-situ spectroscopic ellipsometry with stagnation point flow conditions. An additional advantage is that the proposed cell features a fixed position of the "inlet tube" with respect to the substrate, thus facilitating the alignment of multiple substrates. Theoretical calculations were performed by computational fluid dynamics and compared with experimental data (adsorption kinetics) obtained for the adsorption of polyethylene glycol to silica under a variety of experimental conditions. Additionally, a simple methodology to correct experimental data for errors associated with the size of the measured spot and for variations of mass transfer in the vicinity of the stagnation point is herein introduced. The proposed correction method would allow researchers to reasonably estimate the adsorption kinetics at the stagnation point and quantitatively compare their results, even when using different experimental setups. The applicability of the proposed correction function was verified by evaluating the kinetics of protein adsorption under different experimental conditions.

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Section: Resultsmentioning

confidence: 99%

Determination of a setup correction function to obtain adsorption kinetic data at stagnation point flow conditions

Mora

Nejadnik

Baylon-Cardiel

et al. 2010

Journal of Colloid and Interface Science

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“…Previous studies have shown that hydrodynamic forces are responsible for the removal process of nanoparticles while particle-surface interactions and/or diffusion are responsible for the adsorption process of nanoparticles in QCM-D studies. 36,65,66 Therefore, the removal and adsorption rate constants can display opposite trends with respect to the nanoparticle size as in this study.…”

Section: Model For the Adsorption And Removal Kineticsmentioning

confidence: 61%

“…The Leveque solution has successfully explained various studies involving protein adsorption, 66,70 polymer adsorption, 71,72 copolymer adsorption, 65 and polymer-modied protein adsorption 73 in narrow slits under laminar ow conditions. Therefore, the Leveque solution may also be used for polymeric nanomedicine adsorption and so it is eqn (21), which is a modied Leveque solution that takes into account the curvilinear nature of the ow inside the QCM-D chamber.…”

Section: Mass Transport Of the Nanoparticle Dispersion In The Qcm-d C...mentioning

confidence: 99%

Adsorption and removal dynamics of polymeric micellar nanocarriers loaded with a therapeutic agent on silica surfaces

et al. 2013

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Obtaining a better understanding of the adsorption behavior of polymeric nanomedicines is important to properly assess their distribution and fate and to develop successful strategies for minimizing their distribution in the environment. In this study, the adsorption and removal dynamics of a model polymeric nanomedicine of systematically varied sizeslevofloxacin loaded poly(ethyleneglycol-b-3caprolactone)on and from silica surfaces are investigated using a quartz crystal microbalance with dissipation (QCM-D). For all the sizes of the nanomedicine investigated (90 nm, 110 nm, 149 nm, 174 nm, 207 nm, and 305 nm), the adsorbate mass on the silica followed a roughly exponential trend with respect to time during the exposure stage, suggesting first-order adsorption kinetics. The adsorption rate constant decreased with the increasing particle size. Furthermore, we have developed a modified Leveque equation to describe the mass transport and adsorption behavior of the nanoparticulate dispersion inside the QCM-D chamber. The derivation involved the application of a bipolar coordinate system to the continuity, Navier-Stokes, and convective-diffusion equations. The adsorption rate constants calculated using the derived equation were found to match the experimental results well. The derived equation is important not only in the field of environmental science but also in many other fields as QCM-D is heavily used to characterize the dynamic adsorption behavior of various types of materials including polymers, proteins, and nanoparticles.

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“…The cationic pTMAEMA blocks promote physisorption on negatively charged surfaces and, with appropriate molecular architecture, may produce pMPC end-tethered layers or brushes, as shown schematically in Figure A. Our choice of a cationic anchoring block is motivated by the ubiquitous negative charge on surfaces and the potential for hydrophobic anchoring blocks (useful for hydrophobic surfaces) to micellize in solution, complicating the formation of a uniform adsorbed brush . Nearly monodisperse pMPC-containing diblock copolymers, similar to the polycation-pMPC copolymers synthesized here via reversible addition-fragmentation chain transfer (RAFT) polymerization, were first synthesized by atom-transfer radical polymerization (ATRP) .…”

Section: Introductionmentioning

confidence: 97%

“…Our choice of a cationic anchoring block is motivated by the ubiquitous negative charge on surfaces and the potential for hydrophobic anchoring blocks (useful for hydrophobic surfaces) to micellize in solution, complicating the formation of a uniform adsorbed brush. 40 Nearly monodisperse pMPC-containing diblock copolymers, similar to the polycation-pMPC copolymers synthesized here via reversible addition-fragmentation chain transfer (RAFT) polymerization, were first synthesized by atom-transfer radical polymerization (ATRP). 41 The particular class of p(TMAEMAb-MPC) copolymers in this article was previously synthesized, also by ATRP.…”

Section: ■ Introductionmentioning

confidence: 99%

Adsorbed Polyzwitterion Copolymer Layers Designed for Protein Repellency and Interfacial Retention

et al. 2017

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Poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC), when end-tethered to surfaces by the adsorption of copolymeric cationic segments, forms adsorbed layers that substantially reduce protein adsorption. This study examined variations in the molecular architecture of copolymers containing cationic poly(trimethylammonium ethyl methacrylate (pTMAEMA) anchor blocks that adsorbed strongly to negative surfaces. With appropriate copolymer design, the pTMAEMA blocks were shielded, by pMPC tethers, from solution-phase proteins. The most protein-resistant copolymer layers, eliminating fibrinogen and lysozyme adsorption within detectible limits of 0.01 mg/m, had metrics (the amount of pMPC at the surface and the reduced tether footprint) consistent with the formation of an interfacial polymer brush. The p(TMAEMA-b-MPC) copolymer layers substantially outperformed the protein resistance of surface-polymerized pMPC layers when compared on a per-polyzwitterion-mass basis or on the basis of the scaled tether area. Additionally, p(TMAEMA-b-MPC) copolymer layers offered advantages over the much-studied cationically anchored poly(ethylene glycol) (PEG) graft copolymer system, which forms PEG brushes by the adsorption of a poly l-lysine (PLL) backbone. Although the optimized p(TMAEMA-b-MPC) and PLL-PEG copolymers were similarly fibrinogen-resistant, the cationic protein lysozyme was repelled by pMPC but adhered to the PEG brush via PEG-lysozyme attractions. Additionally, the adsorbed p(TMAEMA-b-MPC) copolymers were not displaced by poly l-lysine homopolymers, which completely displaced the PLL-PEG copolymer to expose a protein-adhesive surface. Thus, the p(TMAEMA-b-MPC) copolymer system comprises a scalable means to produce protein-repellent surfaces, free of the complexities of surface-initiated polymerization and with the advantages of polyzwitterions.

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Adsorption of copolymers aggregates: From kinetics to adsorbed layer structure

Cited by 9 publications

References 51 publications

Determination of a setup correction function to obtain adsorption kinetic data at stagnation point flow conditions

Determination of a setup correction function to obtain adsorption kinetic data at stagnation point flow conditions

Adsorption and removal dynamics of polymeric micellar nanocarriers loaded with a therapeutic agent on silica surfaces

Adsorbed Polyzwitterion Copolymer Layers Designed for Protein Repellency and Interfacial Retention

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